CN113527530B - Preparation method of water-soluble astaxanthin fucoidin ester - Google Patents
Preparation method of water-soluble astaxanthin fucoidin ester Download PDFInfo
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- CN113527530B CN113527530B CN202110901814.2A CN202110901814A CN113527530B CN 113527530 B CN113527530 B CN 113527530B CN 202110901814 A CN202110901814 A CN 202110901814A CN 113527530 B CN113527530 B CN 113527530B
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- astaxanthin
- fucoidin
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- JEBFVOLFMLUKLF-IFPLVEIFSA-N Astaxanthin Natural products CC(=C/C=C/C(=C/C=C/C1=C(C)C(=O)C(O)CC1(C)C)/C)C=CC=C(/C)C=CC=C(/C)C=CC2=C(C)C(=O)C(O)CC2(C)C JEBFVOLFMLUKLF-IFPLVEIFSA-N 0.000 title claims abstract description 145
- 235000013793 astaxanthin Nutrition 0.000 title claims abstract description 145
- 239000001168 astaxanthin Substances 0.000 title claims abstract description 145
- 229940022405 astaxanthin Drugs 0.000 title claims abstract description 145
- MQZIGYBFDRPAKN-ZWAPEEGVSA-N astaxanthin Chemical compound C([C@H](O)C(=O)C=1C)C(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1=C(C)C(=O)[C@@H](O)CC1(C)C MQZIGYBFDRPAKN-ZWAPEEGVSA-N 0.000 title claims abstract description 117
- 150000002148 esters Chemical class 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
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- 239000002808 molecular sieve Substances 0.000 claims abstract description 40
- -1 astaxanthin organic acid diester Chemical class 0.000 claims abstract description 32
- 239000012066 reaction slurry Substances 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 150000007524 organic acids Chemical class 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000011261 inert gas Substances 0.000 claims abstract description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 24
- 235000013305 food Nutrition 0.000 claims description 22
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- 239000011324 bead Substances 0.000 claims description 21
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- 239000002253 acid Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 150000005690 diesters Chemical class 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 13
- 235000006408 oxalic acid Nutrition 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 239000012071 phase Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 5
- WSWCOQWTEOXDQX-UHFFFAOYSA-N 2,4-Hexadienoic acid Chemical compound CC=CC=CC(O)=O WSWCOQWTEOXDQX-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 235000010199 sorbic acid Nutrition 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 2
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- 239000000376 reactant Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 150000002596 lactones Chemical class 0.000 claims 1
- 239000001630 malic acid Substances 0.000 claims 1
- 230000004048 modification Effects 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 9
- HDLNSTQYXPTXMC-UHFFFAOYSA-N Astaxanthin-diacetat Natural products O=C1C(OC(=O)C)CC(C)(C)C(C=CC(C)=CC=CC(C)=CC=CC=C(C)C=CC=C(C)C=CC=2C(CC(C(=O)C=2C)OC(C)=O)(C)C)=C1C HDLNSTQYXPTXMC-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000003094 microcapsule Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 235000016709 nutrition Nutrition 0.000 description 4
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- 241000168517 Haematococcus lacustris Species 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
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- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000855 fermentation Methods 0.000 description 3
- 230000004151 fermentation Effects 0.000 description 3
- 235000013373 food additive Nutrition 0.000 description 3
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000035764 nutrition Effects 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
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- 239000002002 slurry Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- 241000081271 Phaffia rhodozyma Species 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
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- 238000004945 emulsification Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000004291 polyenes Chemical class 0.000 description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- CHQIUNVUTUROQJ-QQXHRLQXSA-N 2,4,4,6-tetramethyl-3-[(1E,3E,5E,7E,9E,11E,13E,15E,17E)-3,7,12,16-tetramethyl-18-(2,4,6,6-tetramethyl-3-oxocyclohexen-1-yl)octadeca-1,3,5,7,9,11,13,15,17-nonaenyl]cyclohex-2-en-1-one Chemical compound O=C1C(C)CC(C)(C)C(\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C=2C(CC(C)C(=O)C=2C)(C)C)=C1C CHQIUNVUTUROQJ-QQXHRLQXSA-N 0.000 description 1
- SWBRTXAKRKRGPH-STWYSWDKSA-N CC=CC=CC(O)=O.C\C=C\C=C\C(O)=O Chemical compound CC=CC=CC(O)=O.C\C=C\C=C\C(O)=O SWBRTXAKRKRGPH-STWYSWDKSA-N 0.000 description 1
- WSWCOQWTEOXDQX-MQQKCMAXSA-N E-Sorbic acid Chemical compound C\C=C\C=C\C(O)=O WSWCOQWTEOXDQX-MQQKCMAXSA-N 0.000 description 1
- 241000239366 Euphausiacea Species 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
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- 239000003963 antioxidant agent Substances 0.000 description 1
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- 150000001514 astaxanthins Chemical class 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000015872 dietary supplement Nutrition 0.000 description 1
- MGJZITXUQXWAKY-UHFFFAOYSA-N diphenyl-(2,4,6-trinitrophenyl)iminoazanium Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1N=[N+](C=1C=CC=CC=1)C1=CC=CC=C1 MGJZITXUQXWAKY-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000002587 enol group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 235000021474 generally recognized As safe (food) Nutrition 0.000 description 1
- 235000021473 generally recognized as safe (food ingredients) Nutrition 0.000 description 1
- 150000004676 glycans Chemical group 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
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- 229940106134 krill oil Drugs 0.000 description 1
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- 230000014759 maintenance of location Effects 0.000 description 1
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- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
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- 125000001483 monosaccharide substituent group Chemical group 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0063—Glycosaminoglycans or mucopolysaccharides, e.g. keratan sulfate; Derivatives thereof, e.g. fucoidan
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
- A23L33/125—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives containing carbohydrate syrups; containing sugars; containing sugar alcohols; containing starch hydrolysates
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
Abstract
The invention belongs to the technical field of astaxanthin water-soluble modification, and particularly relates to a preparation method of water-soluble astaxanthin fucoidin ester. The preparation method comprises the steps of mixing astaxanthin, binary organic acid and a catalyst molecular sieve in water to form a first emulsified and dispersed reaction slurry, reacting the first reaction slurry under the protection of inert gas to obtain an intermediate astaxanthin organic acid diester, mixing the intermediate astaxanthin organic acid diester, fucoidin and the catalyst molecular sieve in water to form a second emulsified and dispersed reaction slurry, and reacting the second reaction slurry under the protection of inert gas to obtain a product astaxanthin fucoidin ester. The solubility of the product astaxanthin fucoidin ester obtained by the preparation method in water is more than 15g/L, thus fundamentally solving the problem of poor water solubility of astaxanthin.
Description
Technical Field
The invention belongs to the technical field of astaxanthin water-soluble modification, and particularly relates to a preparation method of water-soluble astaxanthin fucoidin ester.
Background
Astaxanthin (Astaxanthin, Chinese name 3,3 '-dimethyl-4, 4' -diketo-beta-carotene) with molecular formula C40H52O4The molecule has the polyene long chain structure of carotenoid, has strong active oxygen radical catching capacity and oxidation resistance, and simultaneously has gorgeous red color. Except for medicine, no regulation about application of pure astaxanthin is provided in China at present in the field of food, but haematococcus pluvialis meal is listed in a new resource food catalogue (published by No. 2010-17 of Ministry of health) in 2010, the allowable addition amount is reduced to 12 mg/day of astaxanthin, krill oil is listed in the new resource food catalogue in 2013, the allowable addition amount is 3 g/day, and the allowable addition amount is reduced to about 1.5-3 mg/day of astaxanthin; the swedish bayer's force has been recognized by the FDA in the united states as GRAS certification (No.365), with a daily intake of 4 mg recommended, and with market development and industry development, pure astaxanthin will also grow in the market for food fortification and as a dietary supplement.
At present, the main sources of astaxanthin comprise natural and industrial synthesis, natural astaxanthin has good biological activity, mainly comes from fat of antarctic krill and microbial fermentation (phaffia rhodozyma or haematococcus pluvialis), and astaxanthin is in a free enol structure and is very unstable, and the stability of esterified astaxanthin is improved, but the free astaxanthin and the esterified astaxanthin cannot be dissolved in an aqueous solution. Therefore, the technical problem of poor water solubility of astaxanthin limits the exertion of antioxidant activity (active free radical capture, singlet oxygen quenching and peroxidation free radical resistance) and also limits the utilization efficiency of the astaxanthin in organisms; meanwhile, in the market application, the processing and the diversified application are limited due to the poor water solubility. In conclusion, improving the water solubility of astaxanthin is an important issue for enhancing the in vivo biological activity and commercial feasibility thereof.
Emulsification, microencapsulation and molecular structure modification are common methods for effectively improving astaxanthin solubility, and patent documents 202010097080.2 and 201911297997.0 disclose methods for preparing astaxanthin-containing microcapsules or liquid microcapsules (nano-emulsion), which have general problems of low oil loading rate, poor agglomeration effect, difficulty in controlling solubility, poor application stability and the like, similar to other existing oil and fat microcapsule products, and the problem of astaxanthin water solubility is not solved. In addition, microencapsulation and emulsification both require certain processes and stable conditions, and emulsion breaking or aggregation and precipitation can be caused by heating, electrolyte addition and the like, so that the use effect is influenced, and therefore, the astaxanthin is easily dissolved by modifying the molecular structure, which is a reliable method.
Patent document 1CN201910693039.9 discloses a method for improving astaxanthin solubility by esterifying methoxypolyethylene glycol acetic acid with astaxanthin to bring polyethylene glycol chain with good water solubility, wherein the synthesis method is catalyzed by conventional strong basic catalyst, and pyridine, 4-dimethylaminopyridine, 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride and other toxic and ester-miscible catalysts and solvents are used, and the residue of these organic solvents in the ester is difficult to remove even after multi-step purification; methoxy polyethylene glycol acetic acid is extremely easy to absorb moisture, which causes that astaxanthin ester is easy to absorb moisture and absorb moisture, and methoxy polyethylene glycol acetic acid is not a legal food additive, and the problems bring potential hidden troubles to subsequent food application safety. Patent document 2CN202010733602.3 discloses a method for producing astaxanthin from astaxanthin obtained by breaking cell walls, crushing, centrifuging and the like from concentrated mycelia obtained by fermenting microalgae (haematococcus pluvialis, phaffia rhodozyma and the like) as they are, and separating insoluble components therefrom to obtain a mixed solution in which astaxanthin has good water solubility.
Disclosure of Invention
In order to solve the technical problem of poor water solubility of the astaxanthin in the prior art, the invention provides a preparation method of water-soluble astaxanthin fucoidin ester.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of water-soluble astaxanthin fucoidin ester comprises the steps of mixing astaxanthin, dibasic organic acid and a catalyst molecular sieve in water to form a first emulsified and dispersed reaction slurry, reacting the first reaction slurry under the protection of inert gas to obtain an intermediate diorganoacid astaxanthin diester, mixing the intermediate diorganoacid astaxanthin diester, fucoidin and the catalyst molecular sieve in water to form a second emulsified and dispersed reaction slurry, and reacting the second reaction slurry under the protection of inert gas to obtain the product astaxanthin fucoidin ester.
The binary organic acid is selected from one or more of oxalic acid, succinic acid, 2, 4-hexadienoic acid, fumaric acid, adipic acid, citric acid or 2-hydroxysuccinic acid.
The catalyst molecular sieve is a strong acid molecular sieve; the catalyst molecular sieve is selected from HZSM-5, ZSM5, a modified HZSM-5 molecular sieve modified by element Mo/Si/Zn, or a modified ZSM5 molecular sieve modified by element Mo/Si/Zn; modified molecular sieves having xM2 O:Al2O3:ySiO2:zH2Typical group of O: dXWherein x is 0.7-1.1, y is 5-100, z is 0-40, d is 0-0.1, M is H+，Na+，K+，NH+ 4And X is one or more of Mo/Si/Zn.
The astaxanthin can be natural or synthesized free astaxanthin; the relative molecular weight of the fucoidin is not more than 50000 daltons; the polymerization degree of the fucoidan is not more than 350, namely not more than 350 monosaccharide units.
Preferably, the molar ratio of the dibasic organic acid to the astaxanthin is 5-15: 1; the mass of the catalyst molecular sieve is 2-6% of the total mass of the binary organic acid and the astaxanthin. Mixing the binary organic acid, the free astaxanthin and the molecular sieve together in water with the volume of 1-5 times, adding glass beads with the volume of 5-20% of the total volume of the raw materials, cooling, sanding for 1-5 hours, and filtering out the glass beads to obtain an emulsified and dispersed reaction slurry I formed by the astaxanthin, the binary organic acid, the molecular sieve catalyst and the water.
Preferably, the reaction slurry I is reacted for 3 to 10 hours at the temperature of between 50 and 80 ℃, and inert gas Ar is introduced for protection in the reaction process; and after the reaction is finished, adding 5% NaCl solution with the volume 1-2 times that of the reactant for demulsification, centrifugally separating to remove the solid phase molecular sieve, separating, and reserving an oil phase to obtain the intermediate diorganoic acid astaxanthin diester.
Preferably, the intermediate diorganoic acid astaxanthin diester and fucoidin are mixed together in 1-5 times of volume of water, a molecular sieve is added, glass beads accounting for 5-20% of the total volume of the raw materials are added, sanding is carried out for 1-5 hours under cooling, and the glass beads are filtered to obtain reaction slurry II.
More preferably, the ratio of the mole number of the intermediate diorganoic acid astaxanthin diester to the polymerization degree of the fucoidan is 1:10-30, and the mass of the added molecular sieve is 2-6% of the total mass of the non-aqueous raw materials.
Preferably, the reaction slurry II is reacted for 2-12h at 50-80 ℃, inert gas Ar is introduced for protection in the reaction process, after the reaction is finished, the solid phase molecular sieve is centrifugally separated, the water phase is reserved after liquid separation, and the astaxanthin fucoidin ester is obtained after the solvent is removed and freeze drying is carried out.
The product astaxanthin fucoidin ester prepared by the preparation method comprises an astaxanthin organic acid fucoidin diester a and a fucoidin astaxanthin organic acid lactone b formed on a fucoidin chain; the solubility of the astaxanthin fucoidin ester in water is more than 15g/L, and the astaxanthin content accounts for 3-10% of a or b in terms of mass fraction.
Wherein the astaxanthin organic acid fucoidin diester a contained in the astaxanthin fucoidin ester product and the structure of the fucoidin astaxanthin organic acid lactone b formed on a fucoidin chain are shown as follows:
the astaxanthin fucoidin ester prepared by the preparation method is added into food for application. All the related reagents are allowed to be added into food by food safety regulations, and the product has no toxic substance residue problem and has high food safety.
The invention provides a preparation method of water-soluble astaxanthin ester, which utilizes organic diacid such as oxalic acid for food to link hydroxyl of fucoidin and hydroxyl of free astaxanthin to prepare the product astaxanthin fucoidin ester, wherein the solubility of the product in water is more than 15g/L, thus fundamentally solving the problem of poor water solubility of astaxanthin. The solution of the water solubility of the astaxanthin can lead the astaxanthin to fully exert the antioxidant activity, supplement and enhance the nutritional function of the astaxanthin and expand the utilization efficiency of the astaxanthin in organisms; in market applications, there are a number of processing types and diverse applications that can be broadened due to the water solubility thereof, such as convenience in beverages and liquid phase products. Compared with the prior art, the following specific beneficial effects exist:
1. compared with the disclosed microcapsule technology, the chemical synthesis mode of the invention avoids the problems of application stability and aggregation of the astaxanthin microcapsule and the emulsion, and the relative content of the astaxanthin and the fucoidin in the product can be calibrated by the existing food detection method, thus being beneficial to the compliant application on food;
2. compared with other disclosed chemical synthesis methods for improving the water solubility of astaxanthin, the method disclosed by the invention does not use toxic organic solvents and catalysts, the adopted raw materials are food or food additive raw materials, the product does not have the residue problems of the organic solvents and the catalysts, the whole process is green, the product conforms to food safety regulations, and no potential safety risk exists;
3. compared with other disclosed chemical synthesis methods, the method only uses water as a solvent, the product is simple and feasible to purify, the molecular sieve can be recycled, the production cost can be effectively reduced, the astaxanthin content in the product is 3-10%, and the astaxanthin content in the aqueous solution can reach 15 mg/1 g (the addition amount is about 1-5 mg/100 g of food and beverage required by the existing regulations), so that the application requirement in the technical field of the existing food nutrition fortification can be sufficiently met.
Drawings
FIG. 1 is a UV-Vis spectrum of free astaxanthin according to the invention (Ast in ethanol) and the fucoidan diester of astaxanthin oxalate prepared in example 3 (Ast-Ox-Fuc in water);
FIG. 2 is a FT-IR chart of fucoidan (Fuc) provided by the present invention and the diester of astaxanthin oxalic acid fucoidan (Ast-Ox-Fuc) prepared in example 3;
FIG. 3 is an HPLC chromatogram of astaxanthin (Ast) provided by the present invention and fucoidan (Fuc) and the fucoidan diester of astaxanthin oxalate (Ast-Ox-Fuc) prepared in example 3.
Detailed Description
The invention discloses a preparation method of water-soluble astaxanthin fucoidin ester, which can be realized by appropriately improving process parameters by persons skilled in the art with reference to the content. It is expressly intended that all such similar substitutes and modifications which would be obvious to those skilled in the art are deemed to be included in the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The following detailed description of the invention refers to specific embodiments thereof for better understanding by those skilled in the art.
Example 1
S1Mixing 56 g of hexadienoic acid (sorbic acid), 60 g of free astaxanthin (the molar ratio is 5: 1) and 2.32 g of molecular sieve HZSM-5 (2 percent of the total mass of the raw materials) in about 80mL of water with the volume of 1 time, adding 8mL of glass beads (the total volume is 5 percent), sanding for 1h under cooling, filtering the glass beads to obtain astaxanthin, sorbic acid, a molecular sieve catalyst and water to form uniform reaction slurry;
S2 S1reacting the prepared reaction slurry at 50 ℃ for 10 hours under the protection of Ar gas, adding 90mL (1 time volume) of 5% NaCl solution for demulsification, centrifuging, separating liquid, and reserving oil phase to obtain 49 g of an intermediate, namely the dihexadienoic acid astaxanthin diester, wherein the yield is about 70%;
S349 g S2The prepared intermediate dihexadienoic acid astaxanthin diester, 105 g of fucoidin (the polymerization degree is 300, the ratio of the mole number of the dihexadienoic acid astaxanthin diester to the number of sugar monomers in a fucoidin polymer is 1: 30) and 4.6 g of molecular sieve HZSM-5 (2% of the total mass of the raw materials) are mixed together in 200mL (1-fold volume) of water, 20mL (5% of the total volume) of glass beads are added, sanding is carried out for 1h under cooling, the glass beads are filtered, the slurry is reacted for 12h at 50 ℃, Ar gas is introduced for protection in the reaction process, centrifugation is carried out after the reaction is finished, most of the solvent is removed by reducing pressure after liquid separation, and then freeze drying is carried out to obtain the product astaxanthin hexadienoic acid fucoidin diester 120 g, the yield is about 80% (based on fucoidin), and the astaxanthin content in the product is 3.8% according to the Lambert law.
Example 2
S159 g of succinic acid, 30Mixing free astaxanthin (the molar ratio is 10: 1) and 3.6 g of molecular sieve ZSM-5 (4 percent of the total mass of the raw materials) in 150mL (3 times of the volume) of water together, adding 20mL (10 percent of the total volume) of glass beads, cooling, sanding for 3 hours, filtering the glass beads to obtain astaxanthin, succinic acid, a molecular sieve catalyst and water to form uniform reaction slurry;
S2 S1reacting the prepared reaction slurry at 70 ℃ for 6h, introducing Ar gas for protection in the reaction process, adding 300mL (1.5 times volume) of 5% NaCl solution for demulsification, centrifuging, filtering out glass beads, separating liquid, and reserving oil phase to obtain 21 g of intermediate disuccinic acid astaxanthin diester, wherein the yield is about 60%;
S321 g S2The prepared intermediate disuccinic acid astaxanthin diester, 90 g of fucoidin (the polymerization degree is 200, the ratio of the mole number of the disuccinic acid astaxanthin diester to the number of sugar monomers in a fucoidin polymer is 1: 20) and 4.4 g of ZSM-5 molecular sieve (4 percent of the total mass of the raw materials) are mixed together in 400mL (3 times of volume) of water, 50mL (10 percent of the total volume) of glass beads are added, sanding is carried out for 3 hours under cooling, the glass beads are filtered, slurry is reacted for 8 hours at 70 ℃, Ar gas is introduced for protection in the reaction process, centrifugation is carried out after the reaction is finished, most of solvent is removed by decompression after liquid separation, and then freeze drying is carried out to obtain 77 g of the product astaxanthin succinic acid fucoidin diester, wherein the yield is 70 percent (calculated by fucoidin), and the astaxanthin content in the product is 6.6 percent calculated according to the Lambert law.
Example 3
S1Mixing 54 g of oxalic acid, 24 g of free astaxanthin (the molar ratio is 15: 1) and 6.3 g of molecular sieve HZSM-5 (6 percent of the total mass of the raw materials) in 200mL (5 times of the volume) of water, adding 40mL (20 percent of the total volume) of glass beads, cooling, sanding for 5 hours, filtering out the glass beads to obtain astaxanthin, oxalic acid, a molecular sieve catalyst and water to form uniform reaction slurry;
S2 S1reacting the prepared reaction slurry at 80 ℃ for 3h, introducing Ar gas for protection in the reaction process, adding 500mL (2 times volume) of 5% NaCl solution for demulsification, centrifuging, separating liquid and taking out oil phase, namely21.5 g of the intermediate astaxanthin oxalic acid diester was obtained with a yield of about 80%
S321.5 grams S2The prepared intermediate of the diester of astaxanthin oxalic acid, 144 g of fucoidin (the polymerization degree is 100, the ratio of the diester of astaxanthin oxalic acid to the monomer of fucoidin is 1: 10) and 10 g of molecular sieve HZSM-5 (6% of the total mass of the raw materials) are mixed together in 500mL (5 times of volume) of water, 120mL (20% of the total volume) of glass beads are added, the mixture is sanded for 5h under cooling, the glass beads are filtered, the slurry is reacted for 2h at 80 ℃, Ar protection is needed in the reaction process, centrifugation is carried out after the reaction is finished, most of solvent is removed by water phase under reduced pressure after liquid separation, and then freezing and drying are carried out to obtain 116 g of the diester of astaxanthin oxalic acid fucoidin with the yield of about 80% (calculated by fucoidin). The synthetic route and the main structure of the product astaxanthin oxalic acid fucoidin diester (Ast-Ox-Fuc) are as follows:
the intermediate astaxanthin di-oxalate diester (Ast-Ox) prepared in example 3 has the following structure:
Ast-Ox is a dark red oily liquid, slightly soluble in basic aqueous solution, insoluble in neutral and acidic aqueous solutions, and is characterized as follows: elemental analysis: calculated value C44H52O10C71.33, H7.07, O21.59%, test values: c71.01, H7.30, O21.69%, MALDI-TOF theoretical value: 740.36 (100% molecular ion peak), 741.36 (47.6% isotope peak), test values: 740.36 (100%), 741.35 (47%).
The fucoidan oxalate ester of astaxanthin (Ast-Ox-Fuc) prepared in example 3 was tested in the UV-visible spectrum as shown in FIG. 1, and the main characteristic visible absorption peak of free astaxanthin was located at 496nm in ethanol solution. Since the solution of fucoidan is colorless, no absorption peak in the visible range exists, whereas Ast-Ox prepared in example 3The characteristic absorption peak of astaxanthin also appears in the aqueous solution of-Fuc at 510nm, and the wide absorption peak peculiar to fucoidan also appears near 300-400nm, which indicates that astaxanthin exists on the polymer matrix of fucoidan. Molar extinction coefficient epsilon of test Ast496nm＝1.5×106 g.L-1.cm-1Molar extinction coefficient ε of Ast-Ox-Fuc510nm＝1.6×105g.L-1.cm-1The astaxanthin content in the Ast-Ox-Fuc is about 9.4% as estimated by Lambert's law.
As can be seen from FIG. 2, the Ast-Ox-Fuc was found to be 1768 and 1280cm in comparison with fucoidan-1Shows a characteristic infrared absorption peak of an ester group, 3400--1The hydroxyl absorption peak pattern and position of the polysaccharide are not significantly changed, which suggests that no new carboxyl group is introduced, and the presence of no carboxyl group capable of being neutralized by alkali is verified by the method of alkali titration in chemical analysis, which indicates that the carboxyl group in the astaxanthin monoester is chemically bonded to fucoidan in the form of an ester bond, 1002 and 1100, and 2969cm-1The absorption peak at (A) indicates the presence of a conjugated polyene structure and an olefin C-H bond, which is the characteristic absorption of astaxanthin.
The HPLC spectrum shown in FIG. 3 shows that the retention time of free astaxanthin is about 10.3min, while the peak-off time of the fucoidan used in the example is 32.3min, and that the spectrum of the Ast-Ox-Fuc shows that three peaks of 37-40min correspond to the formation of esters of the diester of astaxanthin with fucoidan with various structural characteristics shown in FIG. 1, and that no peaks corresponding to free astaxanthin or diester of astaxanthin (10-15 min) appear on the chromatographic curve of the Ast-Ox-Fuc, in addition to the peak of unreacted fucoidan observed at 32 min.
In addition, the molecular sieve in the example 3 can be replaced by a modified molecular sieve, other conditions are not changed, the modified molecular sieve is a modified HZSM-5 molecular sieve, and the chemical formula of the molecular sieve is xM2 O:Al2O3:ySiO2:zH2dX-HZSM-5, wherein x is 1, y is 50, z is 20, d is 0.1, M is K+And X is Mo. The yield of product was about 76%, estimated according to Lambert's lawThe astaxanthin content of the Ast-Ox-Fuc was about 8.9%.
Example 4
4.1 the performance advantages of the astaxanthin fucoidan esters prepared in examples 1-3 compared to the previously disclosed astaxanthin ester products are shown in Table 1.
TABLE 1 Properties of the products prepared in examples 1-3 with other astaxanthin products previously disclosed
The data in Table 1 show that the solubility of the intermediate diorgano acid astaxanthin diester of examples 1-3 is low, because there are 10 polyene bonds in the molecular structure of astaxanthin, the two carboxyl groups introduced by the organic acid can not effectively improve the solubility, while the solubility of examples 1-3 is from 15g/L to 29g/L, which indicates that the link of the intermediate and the easily soluble macromolecular fucoidan fundamentally solves the problem of poor water solubility of astaxanthin; the solubility of the product astaxanthin organic acid fucoidin diester in water is inversely proportional to the polymerization degree of fucoidin, which is beneficial to adjustment according to the actual application requirement; the viscosity of the aqueous solution of the astaxanthin organic acid fucoidin diester is in direct proportion to the polymerization degree of fucoidin, and when the polymerization degree of fucoidin is more than 350, the solubility of the product is low and the viscosity is too high, so that the separation in the preparation process is not facilitated. Compared with the astaxanthin ester disclosed by the prior patent, the solubility of the astaxanthin ester prepared by the method disclosed by the invention is equivalent, and the solubility of the water-soluble astaxanthin ester disclosed by the invention completely meets the requirement in consideration of the addition amount of nutrition enhancement in the food industry; in terms of production process, the chemical reagents involved in the method disclosed by the invention are all within the allowable range of food safety standards (GB2760/14880), however, in the comparative example, the problems of fermentation medium residue and the like exist in the astaxanthin fermentation liquor extraction drying mixture, food safety needs to be further verified and discussed, meanwhile, in the comparative example, methoxypolyethylene glycol acetic acid in astaxanthin ester is extremely easy to absorb moisture, so that astaxanthin ester is easy to absorb moisture and absorb moisture, and methoxypolyethylene glycol acetic acid is not a legal food additive, and a large amount of toxic organic solvents and catalysts are used, so the problems all bring potential hazards to subsequent food application safety.
4.2 the antioxidant activity of the fucoidin esters of astaxanthin obtained in examples 1-3 was measured by DPPH radical scavenging test (reference GB/T39100-containing 2020) and singlet oxygen trapping test (reference DOI:10.1016/j. biomaterials.2008.09.061), and the results are shown in Table 2.
Table 2 antioxidant activity of the products of examples 1-3 and their comparison with existing compounds
| IC50* | DPPH free radical | Singlet oxygen |
| Example 1 product (aqueous solution) | 95μg/ml | 1.65mg/ml |
| Example 2 product (aqueous solution) | 92μg/ml | 1.60mg/ml |
| Example 3 product (aqueous solution) | 80μg/ml | 1.35mg/ml |
| Free astaxanthin (ethanol solution) | 75μg/ml | 1.50mg/ml |
| Tea polyphenols (aqueous solution) | 100μg/ml | 2.20mg/ml |
| Fucoidan (aqueous solution) | 5000μg/ml | - |
| 2, 6-Di-tert-butyl-p-cresol (BHT, aqueous solution) | 1.75μg/ml | 15.2μg/ml |
IC50 refers to the concentration of the corresponding compound at which 50% clearance is achieved, based on the pure astaxanthin content
The data in Table 2 show that the astaxanthin esters of the fucoidan of examples 1-3 can be prepared as aqueous solutions, and the solution of water solubility makes the products of examples 1-3 have radical and singlet oxygen scavenging ability comparable to free astaxanthin, which is slightly stronger than tea polyphenols, a commonly used water-soluble food nutrition enhancer, but weaker than BHT, a purely chemically synthesized antioxidant.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of water-soluble astaxanthin fucoidin ester is characterized in that: mixing astaxanthin, dibasic organic acid and a catalyst molecular sieve in water to form a first emulsified and dispersed reaction slurry, reacting the first reaction slurry under the protection of inert gas to obtain an intermediate diorganoic acid astaxanthin diester, mixing the intermediate diorganoic acid astaxanthin diester, fucoidin and the catalyst molecular sieve in the water to form a second emulsified and dispersed reaction slurry, and reacting the second reaction slurry under the protection of inert gas to obtain a product astaxanthin fucoidin ester; the catalyst molecular sieve is selected from HZSM-5, ZSM5, a modified HZSM-5 molecular sieve modified by element Mo/Si/Zn, or a modified ZSM5 molecular sieve modified by element Mo/Si/Zn.
2. The method of claim 1, wherein: the dibasic organic acid is selected from one or more of oxalic acid, succinic acid, 2, 4-hexadienoic acid, fumaric acid, adipic acid and 2-malic acid.
3. The method of claim 1 or 2, wherein: the relative molecular weight of the fucoidan is not more than 50000 daltons; the polymerization degree of the fucoidin is not more than 350.
4. The method of claim 1, wherein: the molar ratio of the dibasic organic acid to the astaxanthin is 5-15: 1; the mass of the catalyst molecular sieve is 2-6% of the total mass of the binary organic acid and the astaxanthin; mixing the binary organic acid, the free astaxanthin and the molecular sieve together in water with the volume of 1-5 times, adding glass beads with the volume of 5-20% of the total volume of the raw materials, cooling, sanding for 1-5 hours, and filtering out the glass beads to obtain an emulsified and dispersed reaction slurry I formed by the astaxanthin, the binary organic acid, the molecular sieve catalyst and the water.
5. The method of claim 1 or 4, wherein: reacting the first reaction slurry at 50-80 ℃ for 3-10h, and introducing inert gas Ar for protection in the reaction process; and after the reaction is finished, adding 5% NaCl solution with the volume 1-2 times that of the reactant for demulsification, centrifugally separating to remove the solid phase molecular sieve, separating, and reserving an oil phase to obtain the intermediate diorganoic acid astaxanthin diester.
6. The method of claim 1, wherein: mixing the intermediate diorganoic acid astaxanthin diester and fucoidin together in water with the volume of 1-5 times, adding a molecular sieve, adding glass beads with the volume of 5-20% of the total volume of the raw materials, sanding for 1-5h under cooling, and filtering the glass beads to obtain reaction slurry II; the ratio of the mole number of the intermediate diorganoic acid astaxanthin diester to the polymerization degree of the fucoidan is 1: 10-30.
7. The method of claim 1 or 6, wherein: and reacting the reaction slurry II at 50-80 ℃ for 2-12h, introducing inert gas Ar for protection in the reaction process, centrifugally separating off the solid-phase molecular sieve after the reaction is finished, separating liquid to leave a water phase, removing the solvent, and freeze-drying to obtain the astaxanthin fucoidin ester.
8. The product astaxanthin fucoidin ester produced by the method of claim 1, wherein: comprises an astaxanthin organic acid fucoidin diester a and an astaxanthin organic acid fucoidin lactone b formed on a fucoidin chain; the solubility of the astaxanthin fucoidin ester in water is more than 15g/L, and the astaxanthin content accounts for 3-10% of a or b in terms of mass fraction.
9. Adding the astaxanthin fucoidin ester prepared by the preparation method of claim 1 into food for application.
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